Major fundamental and applied research results

New type of high-permeable glassy polymers: additive silicon-substituted polynorbornenes and polytricyclononenes

A new type of high-permeable glassy polymers – additive silicon-substituted polynorbornenes and polytricyclononenes – was synthesized in TIPS RAS, characterized by high permeability to gases (e.g. CO₂) as well as to hydrocarbons (C₁-C₄). Effective Ni- and Pd- catalysts were selected which allowed to produce high-molecular polymers (ММ 6-7∙105) with good film-forming and mechanical properties. It has been shown that the gas-separating properties of additive polynorbornenes are improving with an increase in the Me₃Si-substitutes number. Synthesized polytricyclononene with two Me3Si-substitutes along with good gas-separating properties has high chemical stability to the different absorptive liquids in the CO₂ extraction processes, and also thermomechanical stability in rather severe conditions of CO₂ desorption (40 atm, 100°С).

Original process of 1,3-propanediol production

A new original process was developed to produce the important petrochemical product – 1,3-propanediol – the feed for the biodegradable polymer production from glycerin and carbon dioxide. The process includes 3 stages:

• Glycerin and CO₂ transformation to glycerincarbonate, implemented for the first time;
• Glycerincarbonate transformation to glycidol;
• Glycidol hydrogenation to 1,3-propanediol with the 47% selectivily.

The process allows to produce the valuable monomer and to utilize greenhouse gas as well as biodiesel fuel synthesis by-product – glycerin.

Catalytic glycerin and alcohols cross-condensation

The possibility of glycerin involvement to the cross-condensation reaction with alcohols in the presence of the nanostructured Ta-Re catalytic systems was demonstrated for the first time. At the 90% glycerin conversion with the 80-85% yield the C₂-C₁₁ olefins fraction was produced. The reaction seems to be very perspective since it allows to produce the most valuable petrochemical products – wide olefin fraction – from the renewable feed (bioalcohols and bulk waste of the biodiesel fuel production process – glycerin).

TIPS RAS developments prepared or assigned for the implementation

Novel petroleum feed hydroconversion technology

A novel world-unique petroleum feed hydroconversion technology was developed which allows to increase refining depth to 90-92% compared to the traditional 70% of  petroleum refining in Russia.
The process is carried out in a flow unit at Т=420-450°С, Р=6,5-7,5 MPa in the presence of the new-type nanostructured catalyst forming in situ from the precursor. The main process products are C₅-C₁₀ hydrocarbons – high-quality motor fuel components, C₁-C₄ fraction and vacuum gasoil fractions – a valuable feed for petroleum chemistry.
The technology was tested at the pilot units, research data were developed and passed for the technical and economical industrial unit calculation for Taneco plc (Nizhnekamsk town).

Hydroconversion of heavy oils and natural bitumen

The problem of heavy high-viscosity oils and natural bitumen processing is becoming urgent. According to the different estimations the world reserves of little and medium viscosity oils of 162 billion tons (in Russia – 10.8 billion tons) will be sufficient for the next 40-40 years. At the same time there are enormous reserves of high-viscosity oils estimated of 810 billion tons, in Russia – 6.236 billion tons. TIPS RAS developed the original technology of heavy high-viscosity oils and natural bitumen hydroconversion to solve the refining problem. The technology is based on the use of hydroconversion high-active nanosized catalysts forming in situ. The developed technology was tested on the TIPS RAS pilot unit as exemplified by hydroconversion of natural bitumen mixed with wide gasoil fraction. Feed conversion reaches 80%. The obtained product – synthetic oil – contains almost no metals, its desulphurization degree is 50% and it can be processed at a refinery as conventional oil.

Environmentally safe ethylbenzene production process by diethylbenzene transalkylation with benzene

Diethylbenzene is a by-product of the bulk benzene alkylation process with ethylene and its utilization is a critical concern.
TIPS RAS developed the environmentally safe process of diethylbenzene transalkylation with benzene with production of a valuable petrochemical product – ethylbenzene which is used in the styrene production. An original nanostructured process catalyst is developed on the base of zeolite granulated without binders (as distinct from the traditional alkylation catalyst - sulfuric acid). The process is carried out in the conditions similar to the traditional alkylation conditions (Т=200-210°С, Р=2,5MPa) with the 83% diethylbenzene conversion and the 97% selectivity to ethylbenzene. Technical specifications for the catalyst production and the production regulation for Sterlitamaksk catalyst plant were developed. Pilot testing за the transalkylation process was completed and the working regulation was developed for Salavatnefteorgsintez plc.

Catalytic membrane contactor/reactor for deep removal of dissolved oxygen from water

Dissolved oxygen (DO) is one of the major components to be removed for the production of ultra-pure water. Although the concentration of dissolved oxygen in water is very low, approximately 8 ppm (part per million) at ambient temperature, it causes the oxidation of dissolved components and the materials it is contacted with, e.g., the piping of a boiler in the (nuclear) power plant. In the semiconductor industry, the requirements for dissolved oxygen in the ultra-pure rinse water are very low, often less than 1 ppb (part per billion). Also in several other industrial sectors, e.g., in the brewing of beer and in the oil and gas industry (injection water), oxygen removal is important.

Since 1998, TNO and TIPS carried out a joint research projects in the area of catalytic membrane contactor/reactor for deep removal of dissolved oxygen from water.

TNO in conjunction with Topchiev Institute of Petrochemical Synthesis has developed a method of preparation of palladium-loaded polypropylene porous hollow fiber membranes. A patent application is written, which describes a membrane manufacturing procedure for catalytically active layers on commercially available hydrophobic membrane supports. The palladium nanoparticles are placed on the outer membrane surface, whereas the internal pore walls have no catalyst at all.

In catalytic membrane contactor/reactor a gas stream and a liquid stream are supplied on opposite sides of a porous catalytic membrane. However, in contrast to the catalytic diffuser the membrane should possess a good non-wettability. Water is contacting with catalytic side of the membrane but does not penetrate into the pores. The reducing agent is hydrogen, which is fed inside the hollow fibers and diffuses through pores to the outer Pd-coated side of the membranes. Consequently, this system allows good access of both the gas phase and the liquid phase reactants to the catalyst placed on the outer membrane surface and is therefore well suited for hydrogenation reactions in aqueous media.

Palladium deposition method has been scaled up successfully to in-situ coating of membrane modules. Thus, commercially available pilot-scale membrane module (Liqui-Cel contactor) was coated integrally as delivered, without disassembly.

Reduction of dissolved oxygen down to sub-ppb (part per billion) levels possible using developed catalytic membrane contactor/reactor.